Anthraquinone compounds containing the hydroquinonylbenzamido-substituent



United States Patent ANTHRAQUINONE COMPOUNDS CONTAINING THE HYDROQUINONYLBENZAMIDO-SUBSTIT- UENT Arthur D. Jarrett, Watertown, Mass., assignor to Polaroid Corporation, Cambridge, Mass., a corporation of Delaware N0 Drawing. Filed Feb. 15, 1962, Ser. No. 173,339

5 Claims. (Cl. 260377) This invention relates to chemistry and, more particularly, to novel chemical compounds which are useful in preparing monochromatic and multichromatic photographic images.

U.S. Patent No. 2,983,606, issued on May 9, 1961, to Howard G. Rogers, discloses diffusion transfer processes wherein a photographic negative material such as a photographic element, comprising an exposed silver halide emulsion layer containing a latent image, is processed using a compound which is both a dye and a silver halide developer and designated as a dye developer, thereby imparting to the image-receiving element a reversed or positive dye image. In carrying out the process of this patent, a photosensitive element containing a silver halide emulsion is exposed and permeated with a liquid processing composition, for example, by immersing, coating, spraying, flowing, etc., in the dark, and the thus permeated exposed photosensitive element is brought into superposed relationship with an image-receiving layer. In a preferred embodiment, the photosensitive element contains a layer of dye developer and the liquid processing composition permeating the photosensitive element provides a solution of dye developer substantially, uniformly distributed therein. As the exposed silver halide emulsion is developed, the oxidation product of the dye developer is immobilized or precipitated, in situ, with the developed silver, thereby providing an imagewise distribution of unoxidized dye developer dissolved in the liquid processing composition. At least part of the imagewise distribution of unoxidized dye developer is transferred, by imbibition, to the superposed image-receiving layer or element to form the dye transfer image. While the dye developer may be utilized in the photosensitive element, for example, in, on, or behind the silver halide emulsion, it may also be utilized in the image-receiving element or in the liquid processing composition.

The present invention relates to novel dye developers which are particularly useful in photographic processes, products and compositions, such as described above and disclosed with more particularity in the aforementioned US. Patent No. 2,983,606.

One object of this invention, therefore, is to provide novel chemical compounds and novel syntheses for preparing these novel compounds.

Another object ofthe invention is to provide novel chemical compounds useful in photographic products, processes and compositions in which color developing agents are used to develop a latent image.

Yet another object of the invention is to provide novel chemical compounds useful in preparing monochromatic and multichromatic photographic images.

Other objects of the invention will in part be obvious and will in part appear hereinafter.

The invention accordingly comprises the product possessing the features, properties and the relation of components which are exemplified in the following detailed disclosure, and the scope of the application of which will be indicated in the claims.

For a further understanding of the nature and objects of the invention, reference should be had to the following detailed description.

wherein R is hydrogen or an alkyl group, preferably a lower alkyl group, such as, for example, methyl, ethyl, etc.; and R and R may be the same or different or may be hydroxyl or acyloxy groups. The term acyloxy as used herein is meant to signify the grouping wherein R is an aryl, alkyl, aryloxy, or alkoxy group, and the term dye developer as used herein is intended to signify the compounds of Formula (A) wherein both R and R are hydroxyl groups.

It will be apparent that the novel compounds of this invention may also be represented by the formula:

| it i Z N t i B n wherein represents the radical of an anthraquinone dye molecule Z lE-QBZL wherein Z represents the antraquinone dye molecule other than the amino group or groups; n is a positive integer from 1 to 2; and R, R and R have the meanings heretofore noted.

It will be aparent from the foregoing description and the following illustrative examples that the novel compounds of this invention may further be represented by the following formula:

wherein each Q may be hydrogen or an amino, lower alkylamino, lower hydroxyalkylamino, phenylamino, of hydroxyl group; A may be -NH or O; X is lower alkylene; n is a positive integer from 1 to 2; m is a positive integer from I to 2; and R, R and R have the meanings heretofore noted.

3 4 The preferred compounds of this invention are 'ma- (4) H genta dye developers-of the following formula: I l t 7 CH3, OH: (H (D) 11 IIIHOHCHNH-C 1?: (311a H (a N-CH2-R -NC I OH l I OH -NH 0 FEM: A

l 1-[a-metl1yl-B-('3-[2 ',5' '-t lihydr0xypheny1] -benzamido) -pro- H pylamin01-5-anilino anthraqninone wherein R is lower alkylene, preferably containing not CH3 CH3 0 0H more than three carbon atoms, R may be lower alkylene, I II including alicyclic, or arylene, and Y may be hydrogen, 0 NHCFI CHNH C hydroxyl, or I OH? I I g 0H CHrECflEF-lllfi 6 6H l-[a-methyl-fl-(2-methyl-5-[2",5"-dihydroxyphenyl]-benzamido)-pr0pylamino]-5-is0pr0pylamino anthraquinone In the preferred compounds of Formula D, the hydro- (6) CH CH O OH V 3 3 qulnonyl substltuent 1s preferably but not necessarily linked to the phenylene substituent in a position meta to r H- HNH* the carbonyl linkage.

As illustrations of preferred compounds of this invention within the scope of Formula D, mention may be I made of the following magenta dye developers: 7 OH: OH

1 OH CH3 (3H3 (N) /CHNH O o NH-CH-CH-NH-C- CH CHa OH 1-[ a-methyl-JS- 3'42 ,5 '-dihydroxyphenyl] -benza1nido) propylamino1-5- (a-methyl-fi-hydroxy-propylamino) anthraquinone 7 invention,

CH3 r I 4 l-[a-methyl-B-(3-[2,5"-dihydr0xypheny1]-benzamido)- y propylamino]-5-isopropylarnino anthraquinone (2) l. OH

CH3 CH (6 I CH -CH -CH-NH 0 1' a-methyl-fl- 3- [2' ,5 -dihydroxyphenyl] -benzamido) -pro- =pylamin0]-5-a-hydroxymethylpropylamino anthraquinone No. 2,983,606. These compounds exhibit excellent spec-,

tral absorption characteristics and moreover possess particularly good light stability.

While the above-mentioned compounds illustrate the preferred class of dye developers, it will be appreciated that the invention is not limited thereto. As illustrative of other useful anthraquinone dye developers within the scope of Formulae A, B and C, mention may be made of the following novel compounds:

0 OH g l-[a-(3-[2",5"-dihydroxyphenyl]-benzamido)-propy1amino]- 5,8-bis-methylamin0 anthraquiuone pr0p0xy1-anthraquinone The novel anthraquinone dye developers of this invention may be prepared by reacting together, in the presence of a suitable halogen acid acceptor such as, for example, quinoline, anhydrous pyridine, etc., a compound of the formula:

acyloxy II C halogen l aeyloxy 7 and an anthraquinone dye of the formula:

Z-N-H EXAMPLE 1 1 [a-methyl-B- (3 [2",5 "-dihydroxyphenyl -benzamid propy lamina] -5-is0pr0pylamin0 anthraquinone 8 EXAMPLE 2 I a-methyl-B- (3 [2",5 "-dihydroxyphenyl -benzamid0 propyl amino] -5 -u-hydr0xymethylpropylamino anthraquinone 2.0 gm. of l-[fl-amino-a-methyl-propylamino]-5a-hydroxymethylpropylamino anthraquinone were dissolved in 50 ml. of pyridine. 3.0 gm. of 3-diacetoxyhydroquinonyl benzoyl chloride were added and the mixture was then heated at 100 C., "for 35 minutes, after which it was poured into an excess of dilute HCl/ice to precipitate a magenta solid. This solid was filtered, washed with dilute HCl, then with water and dried. It was then dissolved in methyl Cellosolve, deaerated, hydrolyzed with a deaerated sodium hydroxide solution, filtered and treated with carbon dioxide gas, all as in Example 1, to precipitate a magenta powder. This powder'was filtered, washed with water and dried to yield a magenta dye developer, 1 [a methyl 3 (3' [2,5" dihydroxyphenyl] benzamido) propylamino] 5 oz hydroxymethylpropylamino anthraquinone, having the following structural formula:

2.0 gm. of 1-[fi-amino-a-methyl-propylamino]-5-isopro i V pylamino anthraquinone were dissolved in 50 ml. of pyridine. 2.0 gm. of solid 3-diacetoxyhydroquinonyl benzoyl chloride were addedand the resulting mixture was then heated and stirred at just below the reflux temperature for one hour. It was then poured into a dilute HCl/ice mixture and a solid material was precipitated out. This precipitated solid was then filtered, washed with dilute HCl, then washed with water and dried. It was then dissolved in 50 ml. of methyl Cellosolve and the resulting solution was deaerated by bubbling nitrogen through it for 15 minutes. Similarly, a solution of 6.0 gm. of sodium hydroxide in 500 ml. of water was deaerated by bubbling nitrogen through it for 15 minutes. The methyl cellosolve solution was then added to the sodium hydroxide solution under a blanket of nitrogen, and the mixture was stirred at room temperature for one hour to effect complete solution. The solution was then filtered and carbon dioxide gas was bubbled in until a pH of 7-8 was obtained. A magenta powder precipitated and was filtered, washed thoroughly with water and dried in a desiccator to yield 2.7 gm. of a magenta dye developer, 1- [0c methyl 8 (3' [2",5" dihydroxyphenyl] benzarnido)-propylamino]-5-isopropylamino anthraquinone, having the following structural formula:

OH CH3 CH (I) IfH- H-OH-NH-OO I OH 5 I CH-NH 0 C It had a melting point of 144-7 C., exhibited a spectral absorption curve which showed a A at 522 my in methyl Cellosolve: e=12,400. It was soluble in methyl Cellosolve, dimethyl formamide and aqueous sodium-hydroxide, and sparingly soluble in ethyl alcohol and acetone.

It had a melting point of 126-131" C., exhibited a spectral absorption curve which showed a A at 525 m in methyl Cellosolve; e=13,600. It was soluble in methyl Cellosolve, dimethyl formamide and aqueous sodium hydroxide, and sparingly soluble in ethyl alcohol.

EXAMPLE 3 5.0 gm. of 1,5-bis-(B-amino-a-methyl-propylamino)-anthraquinone were dissolved in 150 m1. of pyridine. 15 gm. of 3-diacetoxyhydroquinonyl benzoyl chloride were added and the solution was stirred at 100 C., for minutes, then cooled and poured into an excess of dilute hydroohloric acid/ice mixture. A magenta solid was precipitated out. This solid was filtered, washed with dilute acid, then with water and dried. It was then dissolved in 50 ml. of methyl Cellosolve, deaerated, and added slowly to an oxygen-free solution of 10. gm. of sodium hydroxide in 500 ml. of water, as in the foregoing examples. The mixture was stirred at room temperature for one hour to effect complete solution. Carbon dioxide gas was then bubbled in until a pH of 7-8 was obtained. A magenta solid was precipitated and was filtered, washed with water and dried to yield 2.0 gm. of a magenta dye developer, 1,5 bis [0L methyl B (3' [2",5" dihydroxyphenylJ- 9 benzamido)-propylamino]-anthraquinone, having the following structural formula:

CH3 CH3 CH3 CH3 It had a melting point of 116-121 0, exhibited a spectral absorption curve which showed a A at 5 22 m in methyl Cellosolve; e=12,600. It was soluble in ethyl alcohol, methyl Cellosolve, dimethyl formamide, acetone and aqueous sodium hydroxide.

EXAMPLE 4 1 [ot-methyl-B-(3'-[2",5"-dihydr0xyphenyl] -benzamid propylamino] --anilin0 anthraquinone 700 mg. of 1-(B-amino-u-methyl-propylamino)-5-anilino anthraquinone were dissolved in ml. of pyridine. 2.0 gm. of 3-diacetoxy-hydroquinonyl benzoyl chloride were added and the mixture was heated to 10 C., for 45 minutes, then cooled and poured into an excess of dilute HCl/ ice. A magenta solid was precipitated. This solid was filtered, washed with dilute acid, then with water and dried. It was then dissolved in ml. of methyl Cellosolve hydrolyzed with sodium hydroxide solution under a blanket of nitrogen, as in the foregoing examples. The alkali solution was then filtered and carbon dioxide gas bubbled in until a pH of 7-8 was obtained. A magenta solid precipitated and was washed with water and dried to yield a magenta dye developer, 1-[a-methyl-B-(3- [2",5" dihydroxyphenyl] benzamido) propylamino]- S-anilino anthraquinone, having the following structural formula:

on i R i? l H-CH-GH-NH-CO l-[a-methyl-fi- 3-[2",5"-dihydroxypheny1]-benzarnido) pr0py1amin01-5-aniliuo anthraquinone It had a melting point of 1'05-1;16 0, exhibited a spectral absorption curve which showed a h at 530 m in methyl Cellosolve; e=13,600. It was soluble in aqueous sodium hydroxide, methyl Cellosolve and acetone.

The following examples show by way of illustration and not by way of limitation the photographic utility of the novel compounds of this invention.

EXAMPLE 5 A photosensitive element was prepared by coating a gelatin subcoated film base at a speed of 5 feet/minute with a solution comprising 0.43 gm. of 1-[a-methyl-fi-(3'- [2",5" dihydroxyphenyl] benzamido) propylamino]- 5-isopropylamino anthraquinone dissolved in 10 cc. of 2% cellulose acetate hydrogen ph'thalate in a 50:50 mixture, by volume, of acetone and tetrahydrofuran. After this coating dried, a green-sensitive silver iodobromide emulsion was coated on at a speed of 5 feet/minute and a1- 10 lowed to dry. This photosensitive element was exposed, and processed by spreading between the thus exposed photosensitive element and a superposed image-receiving element, an aqueous processing composition comprising:

The image-receiving element comprised a 2:1 mixture, by weight, of polyvinyl alcohol and poly-4-vinylpyridine on a baryta paper support. After an irnbibition period of approximately one minute, the image-receiving element was separated and contained a magenta positive image.

EXAMPLE 6 The procedure described in Example 5 was repeated, except that the dye developer was dispersed in a layer of gelatin. The coating solution from which the dye developer was coated was prepared by adding 0.67 gm. of the dye developer dissolved in 1 cc. of cyclohexanone and 5 cc. of di(tetrahydrofurfuryl)adipate. This mixture was agitated in a Waring Blendor for two minutes with a solution of 5 gm. of 10% gelatin solution, 1.3 cc. of Water, and 1.0 cc. of Alkanol B. 5 cc. of the resulting dye dispersion was added to 10 cc. of water containing small amounts of saponin and succinaldehyde, and then coated on the gelatin subcoated cellulose acetate film base at a speed of 10 feet/minute.

Substitution of other dye developers described above in the procedures described in Examples 5 and 6 gave similar transfer images.

The dye developers of this invention are also useful in integral multilayer photosensitive elements for use in multicolor diifusion transfer processes. As an example of such photosensitive elements, mention may be made of the photosensitive elements disclosed and claimed in the copending US. application of Edwin H. Land and Howard G. Rogers, Serial No. 565,135, filed February 13, 1956, wherein at least two selectively sensitized photosensitive strata are superposed on a single support and are processed, simultaneously and without separation, with a single common image-receiving element. A suitable arrangement of this type comprises a support carrying a red-sensitive silver halide emulsion stratum, a greensensitive silver halide emulsion stratum and a blue-sensitive silver halide emulsion stratum, said emulsions having associated therewith, respectively, a cyan dye developer, a magenta dye developer and a yellow dye developer. In one of the preferred embodiments of photosensitive elements of this type, the dye developers are disposed in separate alkali-permeable layers behind the photosensitive silver halide emulsion stratum with which they are associated.

The photosensitive elements within the scope of this invention may be used in roll film units which contain a plurality of photosensitive frames. The photosensitive elements of this invention are especially useful in composite roll film intended for use in-a Polaroid Land Camera, sold by Polaroid Corporation, Cambridge 39, Massachusetts, or a similar camera structure such, for example, as the camera forming the subject matter of US. Patent No. 2,435,717, issued to Edwin H. Land on February 10, 1948. In general, such composite roll films comprise a photosensitive roll, a roll of image-receiving material and a plurality of pods containing an aqueous alkaline processing solution. The rolls and pods are so associated with each other that, upon processing, the photosensitive element may be superposed on the imagereceiving element and the pods may be ruptured to spread the aqueous alkaline processing solution between the superposed elements. The nature and construction of the pods used in such units are well known to the art. See, for example, US. Patents Nos. 2,543,181 and 2,634,886, issued to Edwin H. Land.

It will be noted that the liquid processing composition may contain one or more auxiliary or accelerating-silver halide developing agents, such as p-methylaminophenol (Metol); 2,4-diaminophenol (Amidol); benzylaminophenol; hydroquinone; a substituted hydroquinone such as toluhydroquinone, phenylhydr-oquinone, 4'-methy1- phenylhydroquinone; or a 3-pyrazolidone such as lphenyl-3-pyrazolidone. These silver halide developing agents are substantially colorless, at least in their unoxidized form. It is possible that some of the dye developer oxidized in exposed areas may be oxidized by an energy transfer reaction with oxidized auxiliary developing agent.

In addition, development may be effected in the presence of an onium compound, particularly a quaternary ammonium compound, in accordance with the processes disclosed and claimed in the copending application of Milton Green and Howard G. Rogers, Serial No. 50,851, filed August 22, 1960, now US. Patent Serial No. 3,173,786.

The dye developers of this invention may be used also in conventional photographic processes, such as tray or tank development of conventional photosensitive films, plates or papers to obtain black and white, monochromatic or toned prints or negatives. By way of example, a developer composition suitable for such use may come prise an aqueous solution of approximately l2% of the dye developer, 1% sodium hydroxide, 2% sodium sulfiite and 0.05% potassium bromide. After development is completed, any unreacted dye developer is washed out of the photosensitive element, preferably with an alkaline washing medium or other medium in which the unreacted dye developer is soluble. The expression toned is used to designate photographic images wherein the silver is retained with the precipitated dye, whereas monochromatic is intended to designate dye images free of silver.

It should be noted that the dye developers of this medium are self-suflicient to provide the desired color image and do not depend upon coupling reactions to produce the desired color. They thus provide a complete departure from conventional photognaphic color processes in which the color is produced by a coupling reaction between a color former or coupler and the oxidized developing agent, as well as so-called auto-coupling processes in which color is obtained by a reaction of the oxidized developing agent with unoxidized developing agent.

It will be apparent that, by appropriate selection of the image-receiving element from among suitable opaque and transparent materials, it is possible to obtain either a colored positive reflection print or a colored positive transparency. Likewise, the inventive concepts herein set forth are adaptable for multicolor work by the use of special photographic materials, for example, film materials of the type containing two or more photosensitized elements associated with an appropriate number of image receiving elements and adapted to be treated with one or more liquid processing compositions, appropriate dye developers suitable to impart the desired subtractive colors being incorporated in the photosensitized elements or in the liquid processing compositions. Examples of such photographic materials are disclosed in US. Patent No. 2,647,049 to Edwin H. Land.

As examples of us'efulimage-receiving materials, mention may be made of nylon, e.-g., N-methoxymethyl-polyhexamethylene adipamide, polyvinyl alcohol, and gelatin, particularly polyvinyl alcohol or gelatin containing a dye mordant such as poly-4-vinylpyridine. The image-receiving element also may contain a development restrainer, e.g., 1phenyl-S-mercaptotetrazole, as disclosed in the copending application of Howard G. Rogers and Harriet W. Lutes, Serial No. 50,849, filed August 22, 1960.

The dye developers herein set forth are also useful in the formation of colored images in accordance with the photographic products and processes described and claimed in US. 'Patent No. 2,968,554, issued to Edwin H. Land on January 17, 1961.

The novel compounds herein disclosed are also suitable for use as dyes for textile fibres, such as nylon.

.In the preceding portions of the specification, the expression color has been frequently used. This expression is intended to include the use of a plurality of colors to obtain black.

Since certain changes may be made in the above products without departing from the scope of the invention herein involved, it is intended that all matter contained in the above description shall be interpreted as illustrative and not in a limiting sense.

What is claimed is:

1. An anthraquinone dye of the formula:

wherein each Q is selected from the group consisting of hydrogen and amino, lower alkylamino, lower hydroxyalkylamino, phenylamino and hydroxyl groups; A is selected from the group consisting of NH and O; X is lower alkylene; R is selected from the group consisting of hydrogen and lower alkyl; R and R are selected from the group consisting of hydroxyl and acyloxy radicals of the formula:

wherein R is lower alkyl; n is a positive integer from 1 to 2; and m is a positive integer from 1 to 2.

2. l [a methyl 8 (3' [2",5" dihydroxyphenynbenzamido) propylamino] S isopropylamino anthraqumone.

3. 1 [a methyl B (3' [2",5" dihydroxyphenylJ- benzamido) propylamino] 5 a hydroxymethylpropylamino anthraquinone.

4. 1,5 bis [cc methyl B (3' [2",5" dihydroxyphenyl] benzamido) propylamino] anthraquinone.

5. 1 [a methyl B (3' [2",5" dihydroxyphenyl]- benzamido) "-propylamino] 5 anilino anthraquinone.

(References on following page) 1 14 References Cited iy the Examiner 600,463 6/1960 Canada.

2,983,605 5/ 1961 Corlfiy 260377 X Venkataraman, Synthetic Dyes, Vol. 1., pages 358-9 2,983,606 5/1961 Rogers 5 (1952), Academic Press, Inc., N.Y., TP 913 U4 C3.

FOREIGN PATENTS LORRAINE A. WEINBERGER, Primary Examiner. 569,177 1/ 1959 Belgium LEON ZITVER, Examiner.

577,021 6/1959 Canada. 

1. AN ANTHRAQUINONE DYE OF THE FORMULA: 